4,7-Di­chloro-1H-indole-2,3-dione

Golen, J.A.; Manke, D.R.

doi:10.1107/S2414314616014851

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 1| Part 9| September 2016| x161485

doi:10.1107/S2414314616014851

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4,7-Dichloro-1H-indole-2,3-dione

James A. Golen ^a and David R. Manke ^a ^*

^aDepartment of Chemistry and Biochemistry, University of Massachusetts Dartmouth, 285 Old Westport Road, North Dartmouth, MA 02747, USA
^*Correspondence e-mail: dmanke@umassd.edu

Edited by L. Van Meervelt, Katholieke Universiteit Leuven, Belgium (Received 18 September 2016; accepted 20 September 2016; online 23 September 2016)

The title compound, C₈H₃Cl₂NO₂, has a single near-planar molecule in the asymmetric unit, with the non-H atoms having a mean deviation from planarity of 0.042 Å. In the crystal, the molecules dimerize through two N—H⋯O hydrogen bonds. The molecules are further linked through slipped π–π interactions that propagate along the a axis [inter-centroid distance = 3.8639 (10) Å, interplanar distance = 3.3478 (10) Å and slippage = 1.9292 (15) Å].

Keywords: crystal structure; isatin; hydrogen bonding.

CCDC reference: 1505439

Structure description

Herein we report the crystal structure of 4,7-dichloroisatin (Fig. 1). There is a single molecule in the asymmetric unit that has a mean deviation from planarity of only 0.042 Å for the non-H atoms. The bond lengths and angles of the 1H-indole-2,3-dione core are similar to those observed in the parent isatin (Goldschmidt & Llewellyn, 1950 ).

Figure 1
The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radius.

In the crystal, the molecules dimerize through N1—H1⋯O1 hydrogen bonds (Table 1). The molecular packing of the title compound (Fig. 2) also demonstrates parallel slipped π–π interactions that propagate along the a axis [inter-centroid distance = 3.8639 (10) Å, interplanar distance = 3.3478 (10) Å and slippage = 1.9292 (15) Å]. The 4,6-dichloro isomer of this compound does not demonstrate any π–π interactions (Mastrolia et al., 2016 ). The molecules are further linked through C6—H6⋯O2 interactions, which are also observed in the monosubstituted 7-chloroisatin (Sun & Cai, 2010 ). There are C—H⋯Cl interactions present in the structure of 4-chloroisatin (Juma et al., 2016 ), though no intermolecular halogen interactions are observed in the title compound.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86 (1)	2.04 (1)	2.8788 (19)	167 (2)
C6—H6⋯O2ⁱⁱ	0.95	2.43	3.285 (2)	150
Symmetry codes: (i) -x+2, -y+1, -z+1; (ii) $[x-1, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
The molecular packing of the title compound along the a axis, with hydrogen bonds shown as dashed lines.

Synthesis and crystallization

A commercial sample (Matrix Scientific) of 4,7-dichloro-1H-indole-2,3-dione was used for the crystallization. Orange block-shaped crystals were grown by slow evaporation from an acetone solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₈H₃Cl₂NO₂
M_r	216.01
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	120
a, b, c (Å)	3.8639 (10), 13.933 (4), 15.019 (4)
β (°)	93.313 (9)
V (Å³)	807.2 (4)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.76
Crystal size (mm)	0.22 × 0.2 × 0.1

Data collection
Diffractometer	Bruker D8 Venture CMOS
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.702, 0.745
No. of measured, independent and observed [I > 2σ(I)] reflections	29667, 1531, 1415
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.610

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.025, 0.061, 1.08
No. of reflections	1531
No. of parameters	121
No. of restraints	1
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.24
Computer programs: APEX2 and SAINT (Bruker, 2014), SHELXS97 (Sheldrick, 2008 ), SHELXL2014 (Sheldrick, 2015 ), OLEX2 (Dolomanov et al., 2009 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1505439

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616014851/vm4014sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616014851/vm4014Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616014851/vm4014Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009) and publCIF (Westrip, 2010).

4,7-Dichloro-1H-indole-2,3-dione top

Crystal data top

C₈H₃Cl₂NO₂	F(000) = 432
M_r = 216.01	D_x = 1.778 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9837 reflections
a = 3.8639 (10) Å	θ = 3.1–25.7°
b = 13.933 (4) Å	µ = 0.76 mm⁻¹
c = 15.019 (4) Å	T = 120 K
β = 93.313 (9)°	Block, orange
V = 807.2 (4) Å³	0.22 × 0.2 × 0.1 mm
Z = 4

Data collection top

Bruker D8 Venture CMOS diffractometer	1531 independent reflections
Radiation source: Mo	1415 reflections with I > 2σ(I)
TRIUMPH monochromator	R_int = 0.043
φ and ω scans	θ_max = 25.7°, θ_min = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −4→4
T_min = 0.702, T_max = 0.745	k = −16→16
29667 measured reflections	l = −18→18

Refinement top

Refinement on F²	1 restraint
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.025	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.061	w = 1/[σ²(F_o²) + (0.0214P)² + 0.6864P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max = 0.001
1531 reflections	Δρ_max = 0.30 e Å⁻³
121 parameters	Δρ_min = −0.24 e Å⁻³

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.18965 (11)	0.91841 (3)	0.43830 (3)	0.02617 (13)
Cl2	0.46709 (11)	0.52990 (3)	0.24627 (3)	0.02719 (13)
O1	0.9837 (3)	0.59718 (9)	0.58168 (8)	0.0254 (3)
O2	0.6456 (3)	0.78659 (9)	0.58085 (8)	0.0256 (3)
N1	0.7009 (3)	0.58766 (10)	0.44157 (9)	0.0177 (3)
H1	0.778 (5)	0.5327 (7)	0.4261 (12)	0.021*
C1	0.7951 (4)	0.62977 (12)	0.52103 (10)	0.0188 (3)
C2	0.6211 (4)	0.73103 (11)	0.51955 (10)	0.0174 (3)
C3	0.4447 (4)	0.73806 (11)	0.43009 (10)	0.0155 (3)
C4	0.2625 (4)	0.81121 (11)	0.38519 (11)	0.0178 (3)
C5	0.1416 (4)	0.79748 (12)	0.29710 (11)	0.0206 (3)
H5	0.0190	0.8473	0.2658	0.025*
C6	0.2003 (4)	0.71077 (13)	0.25501 (10)	0.0209 (3)
H6	0.1148	0.7017	0.1950	0.025*
C7	0.3826 (4)	0.63658 (11)	0.29914 (10)	0.0176 (3)
C8	0.5044 (4)	0.65116 (11)	0.38626 (10)	0.0152 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0286 (2)	0.0197 (2)	0.0304 (2)	0.00536 (16)	0.00339 (17)	−0.00055 (16)
Cl2	0.0279 (2)	0.0292 (2)	0.0241 (2)	0.00029 (17)	−0.00165 (16)	−0.01124 (17)
O1	0.0297 (6)	0.0260 (6)	0.0195 (6)	0.0056 (5)	−0.0077 (5)	0.0022 (5)
O2	0.0295 (7)	0.0275 (6)	0.0193 (6)	0.0017 (5)	−0.0033 (5)	−0.0058 (5)
N1	0.0194 (7)	0.0164 (7)	0.0169 (6)	0.0016 (5)	−0.0015 (5)	0.0011 (5)
C1	0.0176 (8)	0.0213 (8)	0.0173 (8)	−0.0017 (6)	0.0004 (6)	0.0019 (6)
C2	0.0155 (7)	0.0207 (8)	0.0160 (8)	−0.0017 (6)	0.0001 (6)	0.0011 (6)
C3	0.0133 (7)	0.0188 (8)	0.0145 (7)	−0.0032 (6)	0.0015 (6)	0.0010 (6)
C4	0.0144 (7)	0.0178 (8)	0.0216 (8)	−0.0001 (6)	0.0038 (6)	0.0019 (6)
C5	0.0150 (7)	0.0264 (9)	0.0201 (8)	0.0013 (6)	−0.0008 (6)	0.0077 (7)
C6	0.0153 (7)	0.0338 (9)	0.0133 (7)	−0.0030 (7)	−0.0015 (6)	0.0034 (7)
C7	0.0147 (7)	0.0216 (8)	0.0167 (8)	−0.0032 (6)	0.0015 (6)	−0.0025 (6)
C8	0.0118 (7)	0.0181 (8)	0.0157 (7)	−0.0027 (6)	0.0008 (6)	0.0021 (6)

Geometric parameters (Å, º) top

Cl1—C4	1.7241 (17)	C3—C4	1.391 (2)
Cl2—C7	1.7253 (16)	C3—C8	1.403 (2)
O1—C1	1.2207 (19)	C4—C5	1.391 (2)
O2—C2	1.2024 (19)	C5—H5	0.9500
N1—H1	0.859 (5)	C5—C6	1.388 (2)
N1—C1	1.360 (2)	C6—H6	0.9500
N1—C8	1.406 (2)	C6—C7	1.396 (2)
C1—C2	1.562 (2)	C7—C8	1.380 (2)
C2—C3	1.474 (2)

C1—N1—H1	122.8 (13)	C5—C4—C3	119.56 (15)
C1—N1—C8	110.78 (13)	C4—C5—H5	120.1
C8—N1—H1	125.8 (13)	C6—C5—C4	119.88 (15)
O1—C1—N1	127.74 (15)	C6—C5—H5	120.1
O1—C1—C2	125.75 (14)	C5—C6—H6	119.4
N1—C1—C2	106.50 (13)	C5—C6—C7	121.28 (15)
O2—C2—C1	123.77 (14)	C7—C6—H6	119.4
O2—C2—C3	131.82 (15)	C6—C7—Cl2	121.53 (12)
C3—C2—C1	104.41 (13)	C8—C7—Cl2	120.01 (13)
C4—C3—C2	133.23 (15)	C8—C7—C6	118.44 (15)
C4—C3—C8	119.81 (14)	C3—C8—N1	111.32 (13)
C8—C3—C2	106.87 (13)	C7—C8—N1	127.64 (14)
C3—C4—Cl1	120.14 (12)	C7—C8—C3	121.03 (14)
C5—C4—Cl1	120.30 (12)

Cl1—C4—C5—C6	−179.73 (12)	C2—C3—C8—N1	1.18 (17)
Cl2—C7—C8—N1	0.3 (2)	C2—C3—C8—C7	−177.54 (14)
Cl2—C7—C8—C3	178.74 (11)	C3—C4—C5—C6	0.6 (2)
O1—C1—C2—O2	−3.1 (3)	C4—C3—C8—N1	178.20 (13)
O1—C1—C2—C3	175.86 (15)	C4—C3—C8—C7	−0.5 (2)
O2—C2—C3—C4	3.3 (3)	C4—C5—C6—C7	−0.6 (2)
O2—C2—C3—C8	179.75 (17)	C5—C6—C7—Cl2	−178.14 (12)
N1—C1—C2—O2	178.29 (15)	C5—C6—C7—C8	0.0 (2)
N1—C1—C2—C3	−2.77 (16)	C6—C7—C8—N1	−177.96 (14)
C1—N1—C8—C3	−3.17 (17)	C6—C7—C8—C3	0.5 (2)
C1—N1—C8—C7	175.44 (15)	C8—N1—C1—O1	−175.00 (16)
C1—C2—C3—C4	−175.52 (16)	C8—N1—C1—C2	3.59 (16)
C1—C2—C3—C8	0.94 (16)	C8—C3—C4—Cl1	−179.71 (11)
C2—C3—C4—Cl1	−3.6 (2)	C8—C3—C4—C5	−0.1 (2)
C2—C3—C4—C5	176.01 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86 (1)	2.04 (1)	2.8788 (19)	167 (2)
C6—H6···O2ⁱⁱ	0.95	2.43	3.285 (2)	150

Symmetry codes: (i) −x+2, −y+1, −z+1; (ii) x−1, −y+3/2, z−1/2.

Acknowledgements

We greatly acknowledge support from the National Science Foundation (CHE-1429086).

References

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